CA2199476A1 - Polyester composition - Google Patents

Abstract

A polymer composition comprises (a) a stereospecific, preferably fermentation derived, polyester of molecular weight Mw over 100000 consisting of repeating units of formula - O - CmHn - CO - in which n = 2m and units with m = 3 and m = 4 with respectively a C1 and C2 side group on the carbon atom next to oxygen in the polymer chain are copolymerised together, m being 3 in 70-95 mol percent of such units; and (b) at least one alkyl phenol in which the alkyl group preferably contains at least one tertiary carbon atom adjacent to or within 4 carbon atoms of the phenol nucleus. The alkyl phenol may be hindered and may contain a C1-6 alkoxy group para to the phenolic hydroxy group. Suitable alkyl phenols include 2-tert-butyl-4-hydroxy-anisole and alpha- or delta- tocopherol and others usable as antioxidants in foods, oils and polymer systems. The polyester and alkyl phenol and relative proportions thereof are preferably chosen to provide inhibition of crystallisation of the polyester corresponding to an Avrami 'k' parameter less than 0.03.

Description

~ WO 96107697 0 a ~ ~ 9 4 7 ~ PCT~GB95/02150 POT~ ~K COMPOS 1 -l ' O
THIS lNvkNllON relates to a polyester composition and in particular to a composition comprising an aliphatic polyester and a plasticiser.
Examples of such polyesters have become available co..~ cially as the result of developing microbiological processes for mAk;n~ them. The earliest example, PB, was difficult to melt-process owing to low ~he stability at its melting temperature. Correspon~; n~
copolymers melt at ~ lower temperature. When such polyester is used for making plastics shaped articles, it may be necessary to formulate it with a plasticiser in order to obtain desired mechanical properties. Many plasticising compounds have been proposed for this duty, but there is room for improvement in the mechanical properties obtained and their p~rm~n~nce.
It has now been found that compositions comprising such polyesters (which term is herein to include homopolyesters, copolyesters and mixtures thereof) and one or more phenolic compounds of a defined class show substantial advantages.
ACCORDING TO THE INVENTION in its first aspect a polymer composition comprises (a) a stereospecific polyester of molecular weight Mw over 100000 consisting of repeating units of formula - o - C~ - CO - in which n=2m and units with m=3 and m=4 with respectively a Cl and C2 side group on the c~rhon atom next to oxygen in the polymer chain are copolymerised together, m being 3 in 70-95 mol percent of such units; and (b) at least one alkyl phenol.
In the alkyl phenol there is preferably at least one alkyl group cont~;n;n~ a chain of at least 2 and suitably up to 20 carbon atoms. Preferably at least one such alkyl group contains at least one tertiary carbon atom, for example linked to 2 side substituents other than h~ en, at least one of which atoms is carbon. The chain preferably carries at least 2 and suitably up to 6 hydrocarbon side substituents, and these are preferably Cl6, especially methyl. A or the tertiary carbon atom is W096t07697 ~ 2 ~ ~ 9 4 ~ ~ PCT/GB95/02150 -preferably adjacent to or within 4 carbon atoms of the phenol nucleus. On any of the tertiary carbon atoms, any side substituent atom that is not carbon is preferably oxygen.
The alkyl phenol is preferably ~hin~red~, that is, rotation of the alkyl group is inhibited by collision with a nuclear substituent (especially OH or O-alkyl) ortho to the alkyl group or is prevented by a ring-forming linkage of the alkyl group to the phenolic nucleus.
The alkyl phenol preferably contains also at least one hydrocarbonoxy group, preferably para to the phenolic OH group. Suitably the hydrocarbonoxy group is Cl6 alkoxy.
Particular examples of suitable alkyl phenols are:

2-tert-butyl-4-hydroxyanisole) ) mixture 'BHA' 3-tert-butyl-4-hydroxyanisole) 3,5-di-tert-butyl-4-hydroxytoluene 'BHT' a-tocopherol 'a-T' ~-tocopherol '~-T'.
Instead of the free alkyl phenol, an ester thereof may be present, for example a Cl6 carboxylic ester. It is believed that such ester is an example of a precursor decomposable to the alkyl phenol during processing and/or ageing of the polyester. Likewise, a th~rm~l and/or oxidative reaction product of the alkyl phenol, such as may result from processing and/or ageing, may be added instead of free alkyl phenol. A particular example is 2,2'-dihydroxy-5,5'-dimethoxy-3,3'-di-tert-butylhi~h~n an oxidation product of 3-tert-butyl-4-hydroxyanisole.
The defined class of alkyl phenols includes compounds effective as anti-oxidants, for example in foods, oils and polymer systems. These may be used and are believed to be preferable, especially if they are harmless to life and/or are biodegradable.
The invention includes:
(a) the composition as freshly prepared;
(b) the composition after processing steps short of conversion to finished article;

~ WO 96107697 ~ ~ 9 ~Q 4 7 ~ PCT/GB951021S0 ( c ) f; n; ~~h~ article:
in which there is present the defined alkyl phenol and/or whatever conversion product has been formed from it.
The polyester is preferably capable of a relatively high level of crystallinity, eg over 30%, espec;~lly 50-90~, in the absence of additives.
The molecular weight Mw of the PHA is for example up to eg 2 x 106.
In PHAs having m=3 and m=4 there may be very small, typically fractional, percentages of units having higher values of m. PHA consisting essentially of m=3 units is poly-3-R-hydroxybutyrate (PHB), and PHA consisting of m=3 and 4 units is polyhydroxybutyrate-co-valerate (PHBV).
The PHA can be a product of fermentation, especially a process in which a microorganism lays down PHA during normal growth or is caused to do so by starvation of one or more cell nutrients necessary for cell multiplication.
The microorganism may be wild or mutated or may have the necessary genetic material introduced into it.
Alternatively the necessary genetic material may be harboured by an eukariote. PHA so made is R-stereospecific. Examples of suitable microbiological processes are disclosed in EP-A-69497 (Alcaliaenes eutrogh~
The PHA can be extracted from the fermentation product cells by decomposing non-PHA cellular material leaving microscopic granules Of PHA, or by means of an organic solvent applied to the fermentation product or to such product after one or more steps such as cell breakage or part-decomposition of cellular material. For specialised end-uses cellular material may be partly or wholly allowed to remain with the PHA, but preferably subjected to cell breakage.
Alternatively the PHA can be synthetic, produced for example as described by Bloembergen et al. in Macromolecules 1989, 33. 1656-1663 (PHB) and 1663-1669 (PHBV).

W096/07697 PCTI~L~5J~21S0 -9 ~ 4 7 ~

The polyester component of the composition may contain more than one polyester, for example:
(a) polyesters having the same repeating units but differing in molecular weight; part of the polyester component may be of too low a molecular weight to be usable alone as structural material;
(b) polyesters having different combinations of repeating units;
(c) polyesters of a different class - e.g. synthetic with microbiological - but mutually miscible;
(d) polyester of a different class but not mutually miscible;
(e) polyester, whether or not differing as (a) to (d), having a different history, for example a different manufacturer or extraction procedure or different previous processing such as re-work or recycle or end-group modification.
The alkyl phenol is present in a plasticising proportion, that is, a proportion sufficient in itself to provide, or with other plasticiser(s) to enhance, a plasticising effect. The proportion of alkyl phenol to polyester depends on the intended use of the composition.
The range 2-40 phr w/w includes more of the likely uses.
For making effectively rigid but not brittle articles the range 5-20, especially 6-12, phr w/w is generally suitable.
The polyester, alkyl phenol and relative proportions thereof are preferably chosen to provide at least 30, especially at least 50, percent inhibition of crystallisation of the polyester. Such a composition preferably has an Avrami 'k' parameter less than 0.03, especially less than 0.01. Further, its DSC
crystallisation peak preferably has an area less than 20, especially less than 5, percent of that of the same polyester free of plasticiser.
Such preferred compositions exemplify a new polyester composition defined in terms only of those parameters, and constituting a second aspect of the invention.

~ W096l07697 ~ 4 7 6 PCT~GB9~02~50 The composition may contain components in c~ - use in plastics processing, for example:
(a) one or more other plasticisers other than the defined alkyl phenol;
(b) one or more stabilisers against therm~l or oxidative ~c~mrosition;
tc) inorganic filler, for example glass fibre, carbon fibre, platy or foil particle, silica, clay, ~sgnesium silicate;
(d) organic filler, for example, cellulose fibre or particulate, protein fibre, synthetic polymer particle or fibre, wood flour;
(e) polymer other than polyester;
(f) pigment;
(g) nucleant, especially boron nitride, talc, Amm~n;um chloride or DZBtZn stearate, at preferably 0.2 to 2.0 phr;
(h) volatile solvent for the polyester and alkyl phenol.
If such other plasticiser is present, it may be selected from those already known for these polyesters and/or from any found to plasticise them subsequent to this invention. Examples are:
(a) high boiling esters of polybasic acids, such as phthalates, isophthalates, citrates, fumarates, glutarate, phosphates or phosphites. The esterified radicals may be for example Cl-Cl2 alkyl, aryl or aralkyl. Particular examples are dioctyl-, diheptyl- and diundecyl- phth~l~tes and dialkylalkylene oxide glutarate (Plasthall 7050);
(b) high boiling esters and part-esters of polyhydric alcohols, especially glycols, polyglycols and glycerol. Examples are triacetin, diacetin and glyceryl dibenzoate;
(c) aromatic snlphon~m;des such as paratoluene-Sn 1 phon~m; de.
A particularly preferred plasticiser is a doubly esterified hydroxycarboxylic àcid having at least 3 ester groups in its molecule. 'Doubly esterified' means that at least some of the hydroxy groups of the hydroxy-carboxylic acid are esterified with a carboxylic acid and W096/07697 ~ ~ 9 ~ 9 4 7 ~ PCT/~b5~J~21S0 at least some of the carboxy groups thereof are esterified with an alcohol or phenol. Preferably at least the hydroxycarboxylic acid from which the ester is derived is aliphatic or cycloaliphatic. Its backbone structure (that is, apart from carboxy groups) preferably contains 2-6 carbon atoms. It contA;n~ preferably 2-4 ~rho~y groups and 1-3 hydroxy groups; and preferably the number of carboxy groups exceeds the number of hydroxy groups. An example of such a plasticiser is Estaflex-(acetyltri-n-butyl citrate). 'Trade mark of AKZO.
According to a further aspect of the invention a method of making the composition comprises blending the polyester with the alkyl phenol. This may be effected by for example:
( i ) m; ~; ng the alkyl phenol with the polyester in particulate form, for example in particles smaller than l000, especially smaller than l00, microns.
Preferably the particles are in the size range 0.l to 50 microns. The particles are especially those obtAlne~ by enzymatic removal of non-polyester cell material such as protein from a microbiologically produced biomass. The alkyl phenol can be introduced at any convenient stage, including stages before the particles are isolated from the aqueous medium.
(ii) melting a mixture of polyester with alkyl phenol.
~ The mixture is preferably as made by method ~i).
Other components, for example as in (a) to (d) above, especially those that assist melting, may be present;
(iii) bringing the polyester and alkyl phenol together in a volatile solvent for the polyester. The solvent may have been introduced as a means of extracting the polyester from a microbiologically produced biomass or an int~rm~;ate product from which microbiological cell material has been partly ..Jv~d. Solvent can then be removed or not, according to the requirements of further processing.
Suitable solvents include cyclic carbonate esters and halogenated hydrocarbons such as dichloro-~ W096/07697 ~ PCT1GB95~021S0 methane, chloroform and l,2-dichloroethane.
A particular process comprises:
(i) forming a biomass of ceils cont~in;n~ PHA granules and non-PHA cell material by fermentation;
~ii) tre~ting the biomass to solubilise non-PHA cell material;
(iii) separating the PHA granules from the li~uid phase;
and is characterised by introducing at least one alkyl phenol as hereinbefore defined.
The process may include treating the granules with a peroxide whereby to solubilise non-PHA cell material additional to what has been solubilised in step (ii), and separating the granules from the resulting li~uid phase.
In a yet further aspect the invention provides a process of making a shaped article by confining, eg in a mould or on a surface or through a die, a composition as defined above.
Particular methods include injection moulding, compression moulding, extrusion of fibre or film, extrusion of profile, gas-current spinning, tack spinning, coating on to substrate, any of these being carried out, as appropriate, using the composition in the form of melt, particulate or solution in volatile solvent. Examples of shaped articles made by such methods include films especially for packaging, coated products (such as paper, paperboard and non-woven fabrics), fibres, non-woven fabrics, extruded nets, personal hygiene products, bottles and drinking vessels, agricultural and horticultural films and vessels, slow-release devices and ostomy bags. Alternatively the composition can be used as an adhesive.
The drawings accompanying this specification are as follows:
Figure l : a family of DSC heating curves for control, reference and invention compositions;
Figure 2 : DSC heating curves (a) and cooling curves (b) for pure polyester and composition cont~;n;ng 20phr of BHA.

W096/07697 ~ 9 ~ 7 ~ PCT/GB95/021S0 -The following further data relate to the curves shown in Figure 2.
N~ ~ t~Q~
(a) Heating Peak from : 108.73~C Peak 159.48~C
to : 172.00 Onset 133.72 Jtg 65.14 (b) Cooling Peak from : 23.23~C Peak 52.97~C
to : 82.15 Onset 66.36 J/g 31.04 2 0 ~h V P'~
(a) Heating Peak from : 82.10~C Peak 126.46~C
to: 150.71 Onset :110.17 J/g :35.93 (b) Cooling (No further data) The invention is illustrated by the following experimental data by way of example.
TleST E~2~ u ~ ~ gl~-2 TF-q A
r~OEs.~,l~S OF FRE:SH CO~rCi~.lON
D l ~ 1 ~1 .5cJ~nn ~l ng C~lor~ - tl y ( DSC ) Pr~r~t~on Polyester and plasticiser (if used) (together totalling 1.0g) were dissolved in chloroform (60ml), w~rm~ at 50~C for 10 min, then cast in a stainless steel tray (inside diameter 76.2 mm) and dried under vacuum.
The resulting film was 0.2 to 0.28 mm thick. A speci (ca 4 mg) was cut from the film, placed in each aluminium pan of the DSC instrument and sealed.
DSC ~ t~r~n ,, This techni~ue measures the energy flow towards or from a specimen in comparison with an inert reference as a function of time and temperature. A DSC instrument typically includes two isolated insulated holders on each of which a pan cont~;n~n~ respectively the test specimen ~ WO 96/07697 PCT/ J,,9S,'~,21S0 ~ 2 ~ 7 ~
. 9 or the re~erence is mounted. The heat flow is measured and corqpensated for, to maintain-the temperature with respect to the reference. The instrument can be operated in dynamic mode under a preset temperature ~LO~ ' a~,- or in isoth~ mode.
(i) A Perkin Elmer DSC-2 instL~,e~.t e~Iuipped with a ThPrm~l Analysis Data Station was used in dynamic mode:
Run 1 : heat at 20~C min~l from 20~C to 200~C;
hold at 200~C for 1 min to ensure sample fully melted;
cool at minus 200~C min~l to minus 80~C;
hold at minus 80~C for 10 min to preserve amorphous state.
Run 2 : Finally heat at 20~C min-l from minus 80 to 200~C.
From the measured heat flows the following parameters were derived:
T~, glass transition temperature (run 2);
Tp~1) and Tp(2)peak temperature of melting for the 2 peaks seen;
I~H melting enthalpy.
(ii) The DSC-2 instrument was operated in isothP~l mode as follows:
heat at 20~C min~l from 20~C to 200~C;
hold for 10 min at 200~C to melt;
cool to 57~C rapidly;
hold at 57~C, recording crystallisation peak(s).
The results were analysed by computer loaded with a DSC-2C/4 isoth~ l program, and then further in te~ms of the Avrami equation ~ = exp (-ktn) where ~ is the fraction of uncrystallised material r~m~;nin~ after time t;
- 35 k is a rate constant; and n is the Avrami exponent, which is usually considered to be characteristic of the mode of nucleation.
T--~t Following Japanese Industry Standard K6301, film 0.2 mm thick as made for DSC (see above) was cut into No 3 W096/07697 ~ 2 ~ 9 9 4 7 ~ PCT/GB95/02150 ~

dumbbell pieces of central ~;m~ncions 5 x 20 x 0.2 mm.
These were tested at 0.2 mm sec~l on a TA-XT2 ~h;n~ from Stable Micro Systems, Haslemere, UK.
1 --~
S Polyester compositions were prepared from a PHB of this specification:
structure: PHBV 90:10 copolymer (formula 1, m = 3.1 average);
molecular weight M~477000;
origin: fermentation of glucose + propionic acid by Alcali~nes eutro~hus;
extraction: enzymatic cell-debris removal.
The compositions tested were as follows:
Control - no additive Reference - known plasticiser triacetin TA
Invention - BHA
Invention - BHT
Invention - a-T
Invention - ~-T
Each additive was used at 10, 20 and 30~ w/w, i.e.
11.11, 25 and 42.86 phr.
Results were as follows:
DSC second run dynamic mode results are set out in Table 1. (Note: the ~H values have been recalculated to give energies relative to the amount of polymer present:
the 30~ compositions for example contain only 70~ of polymer).

~ W096/07697 ~ PCT~GB9~02l~
~ ~ ~ 9 g ~ 7 6 Additive T~ Tp2 Tp2 ~ H (cal/g polyesterJ
None -14.3 152.5 161.0 15.1 10% : BHA -18.6 142.2 152.9 11.88 BHT -18.1 144.8 155.3 13.64 a-T -15 . 2 152.7 158.1 15.4 ~-T -17.5 146.6 155.1 14.3 (TA -23.1 143.1 157.7 15.07) 20~ : BHA -26.3 130.7 138.7 6.84 BHT -28.1 134.6 147.5 12.00 a-T -23.6 142.1 153.4 12.48 ~-T -25.8 137.9 151.1 12.48 (TA -40.2 126.2 146.2 12.84) 30~ : BHA -29.9 125.0 0.0 1.56 BHT -33.3 129.3 143.3 13.39 a-T -36.3 138.6 151.3 13.39 ~-T -41.2 135.2 149.8 13.52 (TA -47.9 118.5 140.4 15.21 The following effects are observable:
Ty each invention additive lowers T~, but less strongly than triacetin. The tocopherols appear to give a stronger effect per unit weight of phenolic OH.
Tp: similarly a decrease in melting temperature was seen. This is again characteristic of plasticised systems.
~H: the melting enthalpy is indicative of the level of crystallinity achieved by the polymer during the DSC. The compositions contA;n;ng BHA consistently give lower ~H values suggesting that crystallisation W096/07697 ~ a ~ 9 9 4 7 ~ PCT/GB95/02150 -was being inhibited.
The DSC second run results for compositions contA;n;ng 30~ additive are shown also in Figure l. It is evident that a strong crystallisation exotherm occurs in the unplasticised polyester and in the triacetin composition.
However, this exotherm is weak in the composition contA;n;ng ~T acetate, very weak in the compositions c~ntAin;n~ BHT and ~T, and substantially absent in those cont~;n;ng BHA and aT. It is concluded that plasticisation in the invention compositions is by a merh~n;sm distinct from that effective in the triacetin composition.
This is borne out by the Avrami parameters: the following were calculated:
n k control 2.3 0.368 (triacetin 20% 2.2 0.055) BHA 20% l.8 O.OOl a-T 20~ 2.0 0.004 The k values imply that the rate of recrystallisation of PHBV has been decreased drastically, but the n values show that the mechAn;.cm of recrystallisation is lln~h~nged.
DSC heating (a) and cooling (b) curves for unplasticised polyester and composition contA;n;n~ 20 phr BHA are shown in Figure 2. From the heating curves it is evident that the area under the melting peak is halved by the plasticiser. The cooling curves shown a strong exothenm for unplasticised polyester, but no sign of crystallisation in the composition.
T--nsi lo T---t The effect on elongation-to-break (ETB) is shown in Table 2;

~ W096/~7697 ~ 2 ~ ~ 9 ~ 7 6 PCTJGB9SJD21S~

~bl~ 2 Additive ~ w/w ETB

None 0 l5.9 S (TA l0 23.0 28.0 47.0) BHA l0 31.0 40.0 56.0 a-T lO 25.0 80.0 T$8T r K~ K~ 2 T~ B
r~ ~ OF r~C~r~, 1 ~ S WIT~ T~
The following properties were detPrm;ne~ by standard procedures at 90 days after preparation of the compositions:
Young's modulus (YM) MPa Stress at break (SA~3) MPa Displacement at break (DAB) %
IZOD impact strength (IZOD) Jm~1.
The composition tested consisted of:
PB V copolymer having a B:V molar ratio 93:7 but otherwise similar to the polymer used in the series A tests;
20phr w.w plasticiser (if used);
l phr w/w boron nitride nucleant.
The plasticisers used were:
none (control);
Acetyl-tri-n-butyl-citrate (ATBC) (control) BHA
BHA + ATBC l0 phr w/w each a-T

Results are shown in Table 3.
Tabl~ 3 - Pla~t~
NoneATBC BHA BHA.ATBC a-T
YM1010.0 356.3 280.6 391.1 522.4 SAB24.4 15.0 14.7 16.0 17.2 DAB12.3 25.9 28.8 25.5 25.5 IZOD69.0 224.8 265.8 223.8 125.8 The following conclusions can be drawn:
From YM: the plasticised compositions are distinctly less stiff than the unplasticised composition;
since the BHA/ATBC mixture is less effective than an equal proportion of either plasticiser used alone, it appears that these act by different mechanisms;
a-T is less effective than BHA, but this may be due to its higher molecular weight per phenolic OH (a-T 430, BHA 180).
From SAB and DAB: the invention plasticisers are at least equal to the known ATBC;
From IZOD: BHA and BHA.ATBC are approximately equal but inferior to BHA alone. The lower impact strength using a-T may correlate with its higher molecular weight per phenolic OH.

2 August 1995 .

Claims (2)

1. Polymer composition comprising:
(a) a stereospecific polyester of molecular weight Mw over 100000 consisting of repeating units of formula - O - CmHn - CO - in which n=2m and units with m=3 and m=4 with respectively a C1 and C2 side group on the carbon atom next to oxygen in the polymer chain are copolymerised together, m being 3 in 70-95 mol percent of such units; and (b) at least one alkyl phenol.
Composition according to claim 1 in which the alkyl phenol comprises at least one alkyl group containing a chain of 2-10 carbon atoms and at least one such alkyl group contains at least one tertiary carbon atom.
Composition according to claim 2 in which the tertiary carbon atom is linked to 2 side substituent atoms other than hydrogen, at least one of which atoms is carbon and in which any side substituent that is not carbon is oxygen.
Composition according to any one of the preceding claims in which the chain of the alkyl group carries

2-6 C1-6 alkyl groups as side substituents.
Composition according to claim 4 in which the side substituents are methyl.
Composition according to any one of claims 2 to 5 in which a tertiary carbon atom is adjacent to or within 4 carbon atoms of the phenol nucleus.
Composition according to any one of the preceding claims in which the alkyl phenol is hindered.
Composition according to claim 7 in which the alkyl phenol also contains a C1-6 alkoxy group para to the phenolic hydroxy group.
Composition according to claim 1 in which the alkyl phenol is selected from:
a 2-tert-butyl-4-hydroxyanisole b 3-tert-butyl-4-hydroxyanisole c mixture of a and b d 3,5-di-tert-butyl-4-hydroxytoluene e alpha-tocopherol f delta-tocopherol g 2,2'-dihydroxy-5-5'-dimethoxy-3,3'-di-tert-butylbiphenol Composition according to any one of the preceding claims in which the alkyl phenol is chosen from those usable as antioxidants in foods, oils and polymer systems.
Composition according to any one of the preceding claims in which the polyester has been extracted from fermentation product cells by decomposing non-PHA cellular material leaving microscopic granules of polyester.
Composition according to any one of the preceding claims in which the proportion of alkyl phenol to polyester is in the range 5-20 phr by weight.
Composition according to any one of the preceding claims in which the polyester and alkyl phenol and relative proportions thereof are chosen to provide at least 30, especially at least 40, percent inhibition of crystallisation of the polyester, corresponding to an Avrami 'k' parameter less than 0.03, especially less than 0.02, and a DSC
crystallisation peak of area less than 20, especially less than 5, percent of that of the same polyester free of plasticiser.
Composition according to any one of the preceding claims containing also as further plasticiser a doubly esterified hydroxycarboxylic acid having at least 3 ester groups in the molecule.